A sediment diagenesis model on sediment oxygen demand in managing eutrophication on Taihu, China.

Blue-green algae (CyanoHABs), photosynthetic bacteria that create a harmful aquatic environment, have been a trending issue on Taihu for over a decade. CyanoHABs adapt to varying climatic changes, which explains why the problem on Taihu still thrives. One major drive that keeps the algae is Sediment Oxygen Demand (SOD). In this paper, seasonal and spatial variations of SOD that contribute immensely to nutrient growth in Lake Taihu were done using the Environmental Fluid Dynamics Code (EFDC). The results were analyzed based on Nitrogenous SOD (NSOD) and Total SOD (TSOD). Summer results ranged from - 0.05754 to - 0.0826 (- 0.75658 to - 0.83902) (g/m2/day) and Winter values ranged from - 0.3022 to - 0.40171 (- 1.34486 to - 1.48856) (g/m2/day) indicate a gradual decrease in NSOD (TSOD) values respectively. Relatively higher values in summer are attributed to warmer surface water which sets up thermal stratification to increase the internal loading of nitrogen. Lower winter values are related to inverse stratification, where lower oxygen concentration decreases the SOD to trigger ammonium accumulation in the water column. NSOD (TSOD) values for Autumn results ranged from - 0.1039 to - 0.24786 (- 0.96251 to - 1.39454) (g/m2/day) and Spring values of - 0.43019 to - 0.35959 (- 1.48297 to - 0.54089) (g/m2/day). Transition seasons (i.e., Autumn and Spring) results are impacted by wind mixing that allows dissolved oxygen and nutrients in the whole water column. However, spring values depict a gradual increase in SOD value attributed to spring turnover and gradual stratification, which decrease nutrient concentration. In contrast, decreasing SOD values in autumn are related to mixing, but temperature decreases tend to increase nutrient concentrations. Carbonaceous sediment oxygen demand (CSOD), due to sulfide oxidation, presents high values from the difference between TSOD and NSOD. Based on the high values of CSOD, it is highly recommended that more research on eutrophic Taihu lakes would consider delving into CSOD.

Expansion of the Conceptual Model for the Accumulation of Selenium in Lentic Food Chains to Include Redox-Controlled Generation and Diffusion of Selenite and Dissolved Organo-Selenium Compounds.

The controls governing the availability of reduced selenium (Se) species, namely selenite (Se[IV]) and dissolved organo-Se (DOSe), to primary producers at the sediment-water interface in depositional environments (i.e., lentic systems) were assessed through consideration of theoretical principles and field data. Selenite is generated in suboxic sediment porewater via the microbially mediated reduction of selenate (Se[IV]) and/or reductive dissolution of Se-bearing iron oxides. Field data for lentic environments demonstrate that the production of DOSe in sediment porewaters can also be redox- and depth-dependent. In this manner, the remobilization depths of Se(IV) and DOSe in depositional environments are dependent on the vertical redox gradient (dEh/dz), where deeper depths of remobilization are observed in less reducing sedimentary environments (lower dEh/dz). In turn, remobilization depth has a direct bearing on the concentration of dissolved Se(IV) and DOSe that may be realized at the sediment-water interface because the depth of reaction governs the diffusive path length, concentration gradient, and rate of diffusional transport toward the sediment-water interface. The principles that link sediment redox gradients, depth of remobilization, diffusive transport processes, and concentration of reduced Se species at the sediment-water interface have a direct bearing on the potential for Se uptake by primary producers in lentic food chains (e.g., phytoplankton, biofilms, bacteria). Overall, these processes complement the current conceptual "benthic detrital food chain" model that describes the accumulation of Se in lentic systems. Environ Toxicol Chem 2022;41:2859-2869. © 2022 SETAC.

Nutritional reconstruction in an early modern population: Searching for a relationship between dental microwear and bone element composition.

BACKGROUND: Observing the microwear patterns of the dental crowns enamel surface can provide information on the ingredients and structure of the food consumed, but also on eating habits and lifestyle. Major role in reconstructing the diet and lifestyle of past populations is played by the analysis of alkaline earth metals, such as strontium, barium, zinc and calcium. Ba and Sr are indicators of the consumption of vegetables, plants (cereals and legumes) and marine organisms. This study aims to assess dietary diversity and identify its components based on microscopic techniques and chemical analyses of material from early modern archaeological sites in Wroclaw, Poland. METHODS: The material consisted of 36 permanent molars and the intrasternal parts of 122 first ribs, collected from 6 Wroclaw early modern cemeteries. Tooth microwear was evaluated on Scanning electron microscopy images, with Microwear 4.02 software. Bone chemical composition (Ca, P, Ba, Sr content) was evaluated with mass spectrometry. RESULTS: Most lines were present on the teeth from St. Mary Magdalene Cemetery, with the lowest average number of lines observed on the teeth from St. Barbara Cemetery. The Ca/P ratios calculated for different sites formed two clusters that allows to distinguish two groups of archaeological sites with different bone preservation status. Number of differences in Ba/Sr, Sr/Ca, Ba/Ca ratios was found between disctinct archaeological sites. A number of correlations were found between the concentration of the chemical elements, but no statistically significant correlation was found between the microwear characteristics and the proportion of the elements studied. Some strong correlations were found between microwear features and the Ca/P ratio. CONCLUSIONS: the different values of Sr/Ca, Ba/Ca and Ba/Sr ratios indicate different diets in the different communities. The data obtained indicate a mixed diet, with a relatively high proportion of animal products throughout Wroclaw. Conclusions should be treated with caution due to secondary diagenesis. The lack of interdependence between microwear and chemical composition characteristics suggests that the two methods should be considered complementary and not overlapping, as they provide different insights into the diets of past populations. The comparison of microwear between different sites should always take into account secondary diagenesis and the burial environment, as these influence the characteristics of microwear.

Timescale of reduction of long-term phosphorus release from sediment in lakes.

It is important for lake management and policy to estimate the timescale of recovery from long-term P release from sediment after a reduction in the external load. To provide a scientific basis for this, a condensed model was elaborated, applied and evaluated in four lakes. The model is based on first order kinetics, with an overall rate constant composed of the rate of diagenesis of labile P (kd,2) and rate of burial of P (kb) below an active sediment layer. Using the variation of P fractions in dated sediment cores, kd,2 varied from 0.0155 to 0.383 yr-1, kb from 0.0184 to 0.073 yr-1 and the overall rate constant from 0.0230 to 0.446 yr-1. The active layer depths, 8 to 29 cm, and kd,2 values are within the ranges found by others. The time for a 75% reduction (t75) of labile P in the active layer is 60 years in Lough Melvin, 3 in Ramor, 33 in Sheelin and 41 in Neagh, although P release is only important in Ramor and Neagh. Combining the kd,2 values with other estimates (mean 0.0981 yr-1, median 0.0426; n=14) produces a t75 value of less than 14 and 33 years. A review of other models indicates a timescale of one to two decades and from lake monitoring also of one to two decades. It is desirable to estimate the timescale directly in all lakes if sediment P release is important, but, generally, it should take between one and three decades.

Coupling between sediment biogeochemistry and phytoplankton development in a temperate freshwater marsh (Charente-Maritime, France): Evidence of temporal pattern.

In freshwater systems, sediment can be an important source for the internal loading of PO4. The limiting character of this element in such system leads to consider this phenomenon in terms of eutrophication risks and water quality stakes. A four-months follow-up (January, March, April and May 2019) was carried out in a strong phosphate (PO4) limited secondary channel from an artificial irrigation system of Charente Maritime (France) to link the mobilization of remineralization products in the upper 6 cm layer of sediment (conventional core slicing/centrifugation and DET probes) and the phytoplankton biomass dynamics in the water column. Results showed congruent patterns between the temporal succession of the organic matter mineralization processes in the sediment and the primary biomass dynamics in the water column. In January and March (considered in winter), PO4 proved to be retained by adsorption onto iron oxides in anoxic sediment since pore water nitrate inhibited for about a month the respiration of metal oxides in the first cm of sediment, thus limiting PO4 availability and the phytoplankton growth. In April and May (early spring), after exhaustion of pore water nitrate, the dissolutive reduction of iron oxides released PO4 into pore water generated a significant diffusive outgoing flux from the sediment to the water column with a maximum in April (-1.10E-04±2.81E-05 nmol cm-2 s-1). This release coincided with the nanophytoplankton bloom (5.50 µg Chla L-1) and a potential increase of PO4 concentration in the water column. This work provides some insight on the importance of benthic-pelagic coupling in anthropogenic systems. This conceptual model has to be deployed on other sites of interest where internal loading of P takes precedence over external inputs and nitrate mitigation drives its benthic recycling and ultimately its bioavailability. This is to be essential to characterize the aquatic environment quality in order to limit eutrophication risks.

A Sediment Diagenesis Model of Seasonal Nitrate and Ammonium Flux Spatial Variation Contributing to Eutrophication at Taihu, China.

Algal blooms have thrived on the third-largest shallow lake in China, Taihu over the past decade. Due to the recycling of nutrients such as nitrate and ammonium, this problem has been difficult to eradicate. Sediment flux, a product of diagenesis, explains the recycling of nutrients. The objective was to simulate the seasonal spatial variations of nitrate and ammonium flux. In this paper, sediment diagenesis modeling was applied to Taihu with Environmental Fluid Dynamics Code (EFDC). Latin hypercube sampling was used to create an input file from twelve (12) nitrogen related parameters of sediment diagenesis and incorporated into the EFDC. The results were analyzed under four seasons: summer, autumn, winter, and spring. The concentration of NH4-N in the sediment-water column increased from 2.744903 to 22.38613 (g/m3). In summer, there was an accumulation of ammonium in the water column. In autumn and winter, the sediment was progressively oxidized. In spring, low-oxygen conditions intensify denitrification. This allows algal blooms to continue to thrive, creating a threat to water quality sustainability. The sediment diagenesis model, coupled with water quality measured data, showed an average relative error for Total Nitrogen (TN) of 38.137%, making the model suitable. Future studies should simulate phosphate flux and measure sediment fluxes on the lake.

Chironomid larvae enhance phosphorus burial in lake sediments: Insights from long-term and short-term experiments.

Tube-dwelling macrozoobenthos can affect lake ecosystems in myriad ways, including changes in nutrient fluxes across the sediment-water interface. The pumping activity of chironomid larvae reinforces the transport of solutes between sediment and water. The transport of oxygen into the area surrounding the burrows generates oxidized compounds such as iron(oxy)hydroxides, which results in an additional phosphorus (P) sorption capacity similar to that of oxidized sediment surfaces. In the present study, the effect of the oxidized burrow walls of Chironomus plumosus on P binding capacity and P binding forms was tested in the laboratory using sediments with differing iron contents and varying numbers of chironomid larvae. In an additional long-term experiment, lake sediment naturally rich in iron was incubated under oxic conditions for 165 days, followed by a 3.5-year anoxic period. These experiments showed that: (1) Under oxic conditions the cumulative P uptake by sediments was dependent on larval densities. (2) The P that accumulated both at the sediment-water interface and in the oxidized burrow walls was mainly present as reductive soluble P (iron-bound P). Surprisingly, the amount of P released during the anoxic period in the long-term experiment was independent of the amount of P previously taken up during the oxic period since a portion of P was permanently retained in the sediment. The increase in alkaline soluble metal-bound P (NaOH-SRP) in formerly colonized sediments is a strong indication that the excessive P fixation by reductive soluble iron triggers the subsequent formation of stable iron phosphate minerals such as vivianite. Our study shows that P fixation that is induced by chironomid larvae is not always a completely reversible phenomenon, even after the emergence of the larvae and the re-establishment of anoxic conditions in the sediment.

A combined chemical imaging approach using (MC) LA-ICP-MS and NIR-HSI to evaluate the diagenetic status of bone material for Sr isotope analysis.

This paper presents a combination of elemental and isotopic spatial distribution imaging with near-infrared hyperspectral imaging (NIR-HSI) to evaluate the diagenetic status of skeletal remains. The aim is to assess how areas with biogenic n(87Sr)/n(86Sr) isotope-amount ratios may be identified in bone material, an important recorder complementary to teeth. Elemental (C, P, Ca, Sr) and isotopic (n(87Sr)/n(86Sr)) imaging were accomplished via laser ablation (LA) coupled in a split stream to a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS) and a multicollector inductively coupled plasma mass spectrometer (MC ICP-MS) (abbreviation for the combined method LASS ICP-QMS/MC ICP-MS). Biogenic areas on the bone cross section, which remained unaltered by diagenetic processes, were localized using chemical indicators (I(C)/I(Ca) and I(C) × 10/I(P) intensity ratios) and NIR-HSI at a wavelength of 1410 nm to identify preserved collagen. The n(87Sr)/n(86Sr) isotope signature analyzed in these areas was in agreement with the biogenic bulk signal revealed by solubility profiling used as an independent method for validation. Elevated C intensities in the outer rim of the bone, caused by either precipitated secondary minerals or adsorbed humic materials, could be identified as indication for diagenetic alteration. These areas also show a different n(87Sr)/n(86Sr) isotopic composition. Therefore, the combination of NIR-HSI and LASS ICP-QMS/MC ICP-MS allows for the determination of preserved biogenic n(87Sr)/n(86Sr) isotope-amount ratios, if the original biogenic material has not been entirely replaced by diagenetic material. Graphical abstract ᅟ.

Transhumance pastoralism of Roccapelago (Modena, Italy) early-modern individuals: Inferences from Sr isotopes of hair strands.

OBJECTIVES: In this work, we use Sr isotopes to analyze human hair and determine short-term movements of a contemporary human traveler and of early-modern individuals from an archaeological site (Roccapelago, Modena, Italy, 16th-18th century). MATERIALS AND METHODS: Analyses were performed using a Neptune MC-ICP-MS. We first set up and tested the procedure on scalp hair of a contemporary human, who spent some time between Brazil and Italy. We then analyzed the 87 Sr/86 Sr ratios of eight exceptionally well-preserved archaeological hair specimens associated with human mummies from Roccapelago. Trace elements were analyzed by LA-ICP-MS on single-hair specimens to check the preservation of the archaeological samples. RESULTS: The strontium isotope composition of modern human hair varies from 0.7087 to 0.7093. The 87 Sr/86 Sr ratios of the Roccapelago hair strands range from 0.7082 to 0.7137, with an average of 0.7093 ± 0.0031 (2σ), revealing also intra-individual differences in isotopic composition along the length of the hair shaft. Data were compared with local archaeological rodent bones and teeth and with published isotopic values of water and outcropping rocks. Trace element abundances of archaeological and modern human hair are similarly low in terms of Rare Earth Element (REE) and metal contents, in particular after HNO3 leaching. DISCUSSION: The variable modern human hair 87 Sr/86 Sr ratios show that high-resolution hair sampling tracks the movements of this individual between the two continents. The Sr isotope composition of the mummy hair is consistent with sub-annual human movements from Roccapelago to an area with different 87 Sr/86 Sr ratios. Historical sources indicate that individuals from Roccapelago travelled with their herds to Tuscany for transhumance pastoralism practices. The high radiogenic 87 Sr/86 Sr ratios (>0.71) found in some of the hair are possibly consistent with the Tuscan Magmatic Province and the Tuscan Metamorphic Complex isotope signature. To our knowledge, this is the first study in an archaeological context where the Sr isotope evidence of mobility is corroborated by historical documents.

Nutrient regeneration susceptibility under contrasting sedimentary conditions from the Rio de Janeiro coast, Brazil.

Dissolved silicate (DSi), NH4(+), NO3(-) and PO4(3-) susceptibility to be exchanged between sediment pore waters and overlying waters was evaluated in Jurujuba Sound (JS station) and Coroa Grande Sound (CGS station), southeastern Brazil. Sedimentary elemental (C, N and P) and isotopic (δ(13)C and δ(15)N) compositions evidenced stronger anthropogenic fertilization in JS station. Net NO3(-) influxes from overlying waters occurred, which was two orders of magnitude higher under the more fertilized condition. This condition resulted in 6-13-times higher net effluxes of NH4(+), DSi and PO4(3-) to overlying waters. Vertical alternation between production and consumption processes in pore waters contributed for a more limited regeneration in CGS station. This was associated with diagenetic responses to sedimentary grain size variability in deeper layers and biological disturbance in upper layers. Nearly continuous production of NH4(+), DSi and PO4(3-) in pore waters implied in intensified susceptibility to remobilization under the eutrophic condition of JS station.

Alkalinity production in intertidal sands intensified by lugworm bioirrigation.

Porewater profiles and sediment-water fluxes of oxygen, nutrients, pH, calcium, alkalinity, and sulfide were measured in intertidal sandflat sediments from the Oosterschelde mesotidal lagoon (The Netherlands). The influence of bioturbation and bioirrigation by the deep-burrowing polychaete Arenicola marina on the rates and sources of benthic alkalinity generation was examined by comparing measurements in intact and defaunated sediment cores before and after the addition of A. marina in summer and fall 2011. Higher organic matter remineralization rates, shallower O2 penetration, and greater sediment-water solute fluxes were observed in summer, consistent with higher sediment community metabolic rates at a higher temperature. Lugworm activity stimulated porewater exchange (5.1 × in summer, 1.9 × in fall), organic matter remineralization (6.2 × in summer, 1.9 × in fall), aerobic respiration (2.4 × in summer, 2.1 × in fall), alkalinity release (4.7 × in summer, 4.0 × in fall), nutrient regeneration, and iron cycling. The effects of lugworm activity on net sediment-water fluxes were similar but more pronounced in summer than in fall. Alkalinity release in fall was entirely driven by metabolic carbonate dissolution, while this process explained between 22 and 69% of total alkalinity production in summer, indicating the importance of other processes in this season. By enhancing organic matter remineralization and the reoxidation of reduced metabolites by the sediment microbial community, lugworm activity stimulated the production of dissolved inorganic carbon and metabolic acidity, which in turn enhanced metabolic CaCO3 dissolution efficiency. In summer, evidence of microbial long distance electron transport (LDET) was observed in defaunated sediment. Thus, alkalinity production by net carbonate dissolution was likely supplemented by anaerobic respiration and LDET in summer.